TY  - JOUR
A1  - Hanft, Anna
A1  - Rottschäfer, Dennis
A1  - Wieprecht, Nele
A1  - Geist, Felix
A1  - Radacki, Krzysztof
A1  - Lichtenberg, Crispin
T1  - Aminotroponiminates: Impact of the NO\(_{2}\) Functional Group on Coordination, Isomerisation, and Backbone Substitution
JF  - Chemistry—A European Journal
N2  - Aminotroponiminate (ATI) ligands are a versatile class of redox-active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron-withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro-substituent in the backbone. It is demonstrated that the NO2 group actively contributes to the coordination chemistry of these complexes, effectively competing with the N,N-binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first “naked” (i. e., without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N-coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT-)NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations.
KW  - aminotroponiminates
KW  - non-coordinate anionic ligand
KW  - isomerisation
KW  - electrophilic substitution
KW  - alkali metal
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256988
VL  - 27
IS  - 57
ER  -